JPS63269415A - Manufacture of transparent composite conductor - Google Patents
Manufacture of transparent composite conductorInfo
- Publication number
- JPS63269415A JPS63269415A JP62103168A JP10316887A JPS63269415A JP S63269415 A JPS63269415 A JP S63269415A JP 62103168 A JP62103168 A JP 62103168A JP 10316887 A JP10316887 A JP 10316887A JP S63269415 A JPS63269415 A JP S63269415A
- Authority
- JP
- Japan
- Prior art keywords
- polymer compound
- base material
- transparent
- transparent polymer
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 239000004020 conductor Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000463 material Substances 0.000 claims abstract description 69
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 229920000642 polymer Polymers 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 abstract description 14
- -1 polyethylene terephthalate Polymers 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 4
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract 3
- 239000004793 Polystyrene Substances 0.000 abstract 1
- 229920002223 polystyrene Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 28
- 239000010408 film Substances 0.000 description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000002834 transmittance Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 229910003437 indium oxide Inorganic materials 0.000 description 8
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 7
- 229910001887 tin oxide Inorganic materials 0.000 description 7
- 229920000000 Poly(isothianaphthene) Polymers 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- AZWHFTKIBIQKCA-UHFFFAOYSA-N [Sn+2]=O.[O-2].[In+3] Chemical compound [Sn+2]=O.[O-2].[In+3] AZWHFTKIBIQKCA-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000015 polydiacetylene Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、液晶表示素子等の表示素子、薄膜太陽電池等
の材料として有用な、導電性が高く、光透過性、密着性
および可とう性の良好な透明複合導電体の製造方法に関
する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention is directed to a material having high conductivity, light transmittance, adhesion, and flexibility, which is useful as a material for display elements such as liquid crystal display elements, thin film solar cells, etc. The present invention relates to a method for producing a transparent composite conductor with good properties.
液晶表示等の表示素子、あるいは薄膜太陽電池等におい
ては、可視光透過性が良く、かつ導電性の高い導電膜が
必要不可欠である。BACKGROUND ART In display elements such as liquid crystal displays, thin film solar cells, and the like, conductive films with good visible light transmittance and high conductivity are essential.
従来、透明導電性材料としては、酸化インジウム−酸化
スズ膜（ＩＴＯ膜）や酸化亜鉛、酸化クロム、酸化ホウ
素、酸化ガリウム、酸化アルミニウム等の金属酸化物を
単独または混合して用いるのが一般的であった。これら
の金属酸化物は、基材の中に混合分散させたシ、または
基材の表面に積層したりして用いられている。Conventionally, as transparent conductive materials, it is common to use metal oxides such as indium oxide-tin oxide films (ITO films), zinc oxide, chromium oxide, boron oxide, gallium oxide, and aluminum oxide alone or in combination. Met. These metal oxides are used by being mixed and dispersed in the base material or by being laminated on the surface of the base material.
しかし、前者の方法の場合には、基材の導電性を上げる
には、金属酸化物を基材中に多量に分散させる必要があ
シ、その結果基材の透明性が悪くなるという欠点があっ
た。However, in the case of the former method, in order to increase the conductivity of the base material, it is necessary to disperse a large amount of metal oxide into the base material, which has the disadvantage that the transparency of the base material deteriorates. there were.
一方、後者の方法には、真空蒸着法、スパッタリング法
、イオンプレーテング法など気相中で基材の表面に金属
酸化物の導電層を析出させる物理的方法と化学反応法、
熱分解法等の方法によって基材表面に金属酸化物の導電
層を形成させる化学的堆積方法が知られている。しかし
、これらの方法は、基材の種類、形状等による制限があ
り、各各欠点があった。例えば、真空蒸着法、スノｅッ
タリング法では、多くの場合基材と導電層との密着性が
悪い。また、イオンプレーテング法では、基材の温度が
上がりやすいため、耐熱性に劣る高分子化合物基材は使
用できず、従って使用する基材が限定されるという難点
があった。さらに、化学的反応方法や熱分解法は、基材
表面上の導電層が不均一になシ、導電性を高くすること
が困難であった０
一般的に、金属酸化物を用いた透明導電膜は、可とう性
が少なく、柔軟性に欠けておシ、特に、物理的方法や化
学的堆積方法で基材上に金属酸化物の導電層を積層した
後で、変形した場合、導電層が基材から剥離する場合が
あった。On the other hand, the latter method includes physical methods such as vacuum evaporation, sputtering, and ion plating to deposit a conductive layer of metal oxide on the surface of the substrate in a gas phase, and chemical reaction methods.
A chemical deposition method is known in which a conductive layer of metal oxide is formed on the surface of a substrate by a method such as a pyrolysis method. However, these methods are limited by the type and shape of the base material, and have their own drawbacks. For example, in the vacuum evaporation method and the snortering method, the adhesion between the base material and the conductive layer is often poor. Further, in the ion plating method, the temperature of the base material tends to rise, so a polymer compound base material with poor heat resistance cannot be used, and therefore the base materials that can be used are limited. Furthermore, with chemical reaction methods and thermal decomposition methods, the conductive layer on the surface of the base material is non-uniform, making it difficult to increase the conductivity. Membranes tend to be less flexible and less pliable, especially if they are deformed after depositing a conductive layer of metal oxide on a substrate by physical or chemical deposition methods. may peel off from the base material.
これらの欠点を改良する方法として、例えばマグネトロ
ンカソードの中心部に基体を通過させる穴（貫通口）を
設け、基体を酸化亜鉛の焼結体等の表面に対して垂直に
配置してマグネトロンスノクッタリングを行なう方法（
特開昭６１−２６３００８号公報）、支持体上に酸化イ
ンジウムおよび酸化スズのいずれか一方を含む透明導電
層を積層して、長さ方向および幅方向のいずれの方向に
おいても熱収縮性を有する透明導電性フィルムを得る方
法（特開昭６１−２７９００３号公報）、基板上に高周
波ス・ぐツタリングによシ透明導電膜を形成する方法に
おいて、ターゲットに酸化インジウムを用い、プレナー
マグネトロン方式による高周波スノぐツタリングを行な
って基板上に酸化インジウム導電膜を形成し、次いでア
ニーリングを行ない、その後スミ４ツタエツチングする
方法（特開昭６１−２９０６０５号公報）等のごとき物
理的方法が提案されている。As a method to improve these drawbacks, for example, a hole (through hole) through which the substrate passes is provided in the center of the magnetron cathode, and the substrate is placed perpendicular to the surface of a sintered body of zinc oxide, etc. How to do a ring (
JP-A No. 61-263008), a transparent conductive layer containing either indium oxide or tin oxide is laminated on a support and has heat shrinkability in both the length direction and width direction. A method for obtaining a transparent conductive film (Japanese Unexamined Patent Publication No. 61-279003), a method for forming a transparent conductive film on a substrate by high-frequency struttering, using indium oxide as a target and using high-frequency waves using a planar magnetron method. Physical methods have been proposed, such as a method in which an indium oxide conductive film is formed on a substrate by snog etching, followed by annealing, and then corner etching (Japanese Patent Application Laid-open No. 290605/1983).
しかし、これらの方法は、上記欠点の改良方法としては
いまだ十分満足すべき方法ではない。However, these methods are still not fully satisfactory as methods for improving the above-mentioned drawbacks.
本発明の目的は、前記従来技術の欠点を克服して、導電
性が高く、光透過性１表面均一性、可とう性および密着
性にすぐれた透明複合導電体の製造方法を提供すること
にある。An object of the present invention is to overcome the drawbacks of the prior art and provide a method for producing a transparent composite conductor that has high conductivity, light transmittance, surface uniformity, flexibility, and adhesion. be.
本発明によって上記目的を達成し得る透明複合導電体の
製造方法が提供される。The present invention provides a method for manufacturing a transparent composite conductor that can achieve the above object.
即ち、本発明は、透明高分子化合物基材上に、該基材を
溶解可能な有機溶媒、導電性高分子化合物および金属酸
化物からなる混合物または該基材を溶解可能な有機溶媒
、導電性高分子化合物、金属酸化物および前記透明高分
子化合物基材を構成する材料からなる混合物を塗布し、
次いで溶媒を除去することを特徴とする透明複合導電体
の製造方法に関する。That is, the present invention provides an organic solvent capable of dissolving the base material, a mixture consisting of a conductive polymer compound and a metal oxide, or an organic solvent capable of dissolving the base material, a conductive Applying a mixture consisting of a polymer compound, a metal oxide, and a material constituting the transparent polymer compound base material,
The present invention relates to a method for producing a transparent composite conductor, which comprises subsequently removing the solvent.
以下、本発明の透明複合導電体の製造方法について説明
する。Hereinafter, the method for manufacturing the transparent composite conductor of the present invention will be explained.
本発明において用いられる透明高分子化合物基材を構成
する材料としては、光透過率が高く、柔軟性を有し、薄
膜化できるものであれば特に限定されるものでなく、代
表例としてはポリエチレンテレフタレートなどのポリエ
ステル、２リスチレン、ポリエチレン、ポリプロピレン
、Ｉす塩化ビニル、虜り塩化ビニリデン、ポリカーボネ
ート。The material constituting the transparent polymer compound base material used in the present invention is not particularly limited as long as it has high light transmittance, is flexible, and can be made into a thin film, and a typical example is polyethylene. Polyesters such as terephthalate, 2-listyrene, polyethylene, polypropylene, vinyl chloride, vinylidene chloride, polycarbonate.
アセテート、ポリアミド、ポリイミド、ポリメチルメタ
アクリレート、ポリスルホン、ポリエーテルサルホン、
ナイロン等があげられる。これらの透明高分子化合物基
材を構成する材料は、使用方法、目的に応じて適宜選択
することができる。Acetate, polyamide, polyimide, polymethyl methacrylate, polysulfone, polyethersulfone,
Examples include nylon. The materials constituting these transparent polymer compound base materials can be appropriately selected depending on the usage method and purpose.
本発明でいう基材とは、フィルム、シート等の膜状物で
あシ、その厚さは使用目的に応じて適宜選択される。The base material referred to in the present invention is a membrane-like material such as a film or a sheet, and the thickness thereof is appropriately selected depending on the purpose of use.
透明高分子化合物基材を溶解可能な有機溶媒としては、
透明高分子化合物基材の良溶媒であればイスレテモヨく
、代表例としてはベンゼンのごとき芳香族炭化水素類、
塩化メチレン、四塩化炭素等のごときハロゲン化合物類
、テトラヒドロフランのごときエーテル類、アセトンの
ごときケトン類等があげられる。これらの有機溶媒は、
使用する透明高分子化合物基材の種類によって適宜選択
される。また、有機溶媒は、１種または２種以上混合し
て使用してもよい。Organic solvents that can dissolve transparent polymer compound base materials include:
If it is a good solvent for a transparent polymer compound base material, it is suitable for use. Typical examples are aromatic hydrocarbons such as benzene,
Examples include halogen compounds such as methylene chloride and carbon tetrachloride, ethers such as tetrahydrofuran, and ketones such as acetone. These organic solvents are
It is appropriately selected depending on the type of transparent polymer compound base material used. Further, the organic solvents may be used alone or in combination of two or more.
上記有機溶媒（良溶媒）は、それ自体単独で使用しても
よく、また透明高分子化合物基材を溶解可能な範囲内で
、該基材の貧溶媒と混合して使用してもよい。本発明で
は、これら両者を含めて透明高分子化合物基材を溶解可
能な有機溶媒という。The above-mentioned organic solvent (good solvent) may be used alone or may be used in combination with a poor solvent for the transparent polymer compound base material within a range that can dissolve the base material. In the present invention, both of these solvents are referred to as organic solvents capable of dissolving the transparent polymer compound base material.
貧溶媒としては、使用する透明高分子化合物基材を溶解
せず、かつ良溶媒と良く混合できる有機溶媒であればい
ずれでもよい。このような貧溶媒としては、例えばメチ
ルアルコール、エチルアルコール等のアルコール類、水
等があげられる。貧溶媒は、用いられる透明高分子化合
物基材、良溶媒の種類によって組合せが選択される。Any organic solvent may be used as the poor solvent as long as it does not dissolve the transparent polymer compound base material used and can be mixed well with a good solvent. Examples of such poor solvents include alcohols such as methyl alcohol and ethyl alcohol, and water. The combination of poor solvents is selected depending on the transparent polymer compound base material used and the type of good solvent.
良溶媒と貧溶媒からなる混合溶媒中に占める貧溶媒の割
合は、用いる透明高分子化合物基材、導電性高分子化合
物および良溶媒の種類によって異なるので一部には決め
られないが、一般には混合溶媒中長くとも３０容量チ、
好ましくは１０容量チの範囲内であれば、透明高分子化
合物基材を溶解可能である。混合溶媒中に占める貧溶媒
の割合が３０容量チよシ多い場合は、透明高分子化合物
基材を溶解することが困難となシ、透明高分子化合物基
材と、導電性高分子化合物および金属酸化物または導電
性高分子化合物、金属酸化物および透明高分子化合物基
材を構成する材料との密着性に劣る。本発明においては
、透明高分子化合物基材を溶解可能な有機溶媒を使用す
るため、基材表面が一部溶解して基材が導電性高分子化
合物および金属酸化物、または導電性高分子化合物、金
属酸化物および透明高分子化合物基材を構成する材料を
包含した形となり、基材と、導電性高分子化合物、金属
酸化物等からなる導電膜との密着性が強固なものとなる
。The proportion of the poor solvent in a mixed solvent consisting of a good solvent and a poor solvent cannot be determined in part because it varies depending on the type of transparent polymer compound base material, conductive polymer compound, and good solvent used, but in general At most 30 volumes in the mixed solvent,
The transparent polymer compound base material can be dissolved preferably within the range of 10 volumes. If the proportion of the poor solvent in the mixed solvent is more than 30 volumes, it will be difficult to dissolve the transparent polymer compound base material, and the transparent polymer compound base material, the conductive polymer compound, and the metal. Poor adhesion to materials constituting the oxide or conductive polymer compound, metal oxide, and transparent polymer compound base material. In the present invention, since an organic solvent that can dissolve the transparent polymer compound base material is used, the surface of the base material is partially dissolved and the base material becomes a conductive polymer compound and a metal oxide, or a conductive polymer compound. , the metal oxide and the material constituting the transparent polymer compound base material are included, and the adhesion between the base material and the conductive film made of the conductive polymer compound, metal oxide, etc. becomes strong.
本発明において用いられる導電性高分子化合物とは、Ｔ
電子共役構造を有する高分子化合物のことであり、電気
伝導度が１ＯＳ／ｃｒｎ以上、好まし′くはｌ ０−３
８／ｃ１ｎ以上の値を有するものが望ましい。The conductive polymer compound used in the present invention is T
It refers to a polymer compound having an electronic conjugated structure, and has an electrical conductivity of 1OS/crn or more, preferably 10-3
It is desirable to have a value of 8/c1n or more.
このような導電性高分子化合物の例としては、ポリアセ
チレン、ポリパラフェニレン、ポリピロール。Examples of such conductive polymer compounds include polyacetylene, polyparaphenylene, and polypyrrole.
ポリチオフェン、ポリシアノアセチレン、ポリインチア
ナフテン、ポリジアセチレン、ポリアニリン。Polythiophene, polycyanoacetylene, polyinthianaphthene, polydiacetylene, polyaniline.
ポリフタロシアニンおよびこれらの誘導体をあげること
ができる。これらの中で好ましい導電性高分子化合物と
しては、ポリチオフェン、ポリインチアナフテン、ポリ
ピロールがあげられ、さらに好ましくはポリインチアナ
フテンがあげられる。Mention may be made of polyphthalocyanines and their derivatives. Among these, preferable conductive polymer compounds include polythiophene, polyinthianaphthene, and polypyrrole, and more preferably polyinthianaphthene.
ポリインチアナフテン（以下、ＰＩＴＮと略称する）、
は、特開昭６１−１７５８１号公報や特開昭６１−１２
７８４号公報に開示されているごとく、中性状態（アン
ドープ状態）において約１０−２８／ｃｍの電気伝導度
を有しておシ、ドープ後においては、１０Ｓ／ａｎ以上
の電気伝導度を示す高導電性高分子化合物である。また
、このＰＩＴＮは、膜厚ｏ、１５μｍで光透過率が７０
％以上であって、透明性の良い導電性高分子化合物であ
る。Polyinthianaphthene (hereinafter abbreviated as PITN),
JP-A-61-17581 and JP-A-61-12
As disclosed in Publication No. 784, it has an electrical conductivity of about 10-28/cm in a neutral state (undoped state), and shows an electrical conductivity of 10 S/an or more after doping. It is a highly conductive polymer compound. Moreover, this PITN has a film thickness o of 15 μm and a light transmittance of 70
% or more, and is a conductive polymer compound with good transparency.
従って、このＰＩＴＮは、透明導電性膜の材料として極
めて有用な材料である。Therefore, this PITN is an extremely useful material for transparent conductive films.
ＰＩＴＮＯ裂遣方法としては、インチアナフテン（ＩＴ
Ｎ ）モノマーの電解重合法や化学重合法のいずれの方
法を採用してもよいが、化学重合法によって粉末状のＰ
ＩＴＮを製造することが工業的には有利である。As for the PITNO splitting method, inchianaphthene (IT
N) Either the monomer electrolytic polymerization method or the chemical polymerization method may be used, but the chemical polymerization method
It is industrially advantageous to produce ITN.
本発明において用いられる金属酸化物としては、酸化イ
ンジウム、酸化スズ、酸化亜鉛、酸化クロム、酸化ホウ
素、酸化ガリウム、酸化アルミニウム、酸化アンチモノ
等があげられる。これらの金属酸化物は、１種または２
種以上を混合して使用してもよい。Examples of metal oxides used in the present invention include indium oxide, tin oxide, zinc oxide, chromium oxide, boron oxide, gallium oxide, aluminum oxide, and antimono oxide. These metal oxides may be one or two types.
You may use a mixture of more than one species.
導電性高分子化合物および金属酸化物と併用される透明
高分子化合物基材を構成する材料は、前記した透明高分
子化合物基材を構成する材料と同様なものである。透明
高分子化合物は、基材を構成する材料と同じであっても
または異なってもよいが、基材との密着性を良好にする
ためには基材と同一材料であることが好ましい。基材を
構成する材料を配合することにより、混合物の粘度を調
節することができ、種々な塗布方法に対応できるう透明
高分子化合物基材を溶解可能な有機溶媒。The material constituting the transparent polymer compound base material used in combination with the conductive polymer compound and the metal oxide is the same as the material constituting the transparent polymer compound base material described above. Although the transparent polymer compound may be the same as or different from the material constituting the base material, it is preferably the same material as the base material in order to improve adhesion to the base material. An organic solvent that can dissolve a transparent polymer compound base material and allows the viscosity of the mixture to be adjusted by blending the materials that make up the base material, making it compatible with various coating methods.
導電性高分子化合物、°金属酸化物および透明高分子化
合物基材を構成する材料の混合割合は、混合物総重量中
、有機溶媒が５〜５０重量％、好ましくは１０〜４０重
量％、導電性高分子化合物が２０〜９０重量％、好まし
くは３０〜８０重量％、金属酸化物が５〜５０重量％、
好ましくは１０〜３０重量％、透明高分子化合物基材を
構成する材料がＯ〜３０ｉ量チ、好ましくＦｉＯ−１５
重量多であることが好ましい。The mixing ratio of the materials constituting the conductive polymer compound, the metal oxide, and the transparent polymer compound base material is that the organic solvent is 5 to 50% by weight, preferably 10 to 40% by weight, based on the total weight of the mixture. 20 to 90% by weight of a polymer compound, preferably 30 to 80% by weight, 5 to 50% by weight of a metal oxide,
Preferably 10 to 30% by weight, the amount of material constituting the transparent polymer compound base material is O to 30%, preferably FiO-15
Preferably, it is heavy.
上記各成分の混合は、温度１時間、方法については特に
制限はなく、一般には室温で攪拌を行なえば充分である
。There are no particular restrictions on the method for mixing the above components at a temperature of 1 hour, and stirring at room temperature is generally sufficient.
混合物は、均一溶液、スラリー状またはペースト状であ
ってもよい。The mixture may be in the form of a homogeneous solution, slurry or paste.
このようにして得られた混合物は、次に透明高分子化合
物基材上に塗布する。混合物を塗布した後は平坦化し、
次いで溶媒を除去することによって透明複合導電体とす
ることができる。The mixture thus obtained is then applied onto a transparent polymeric compound substrate. After applying the mixture it is flattened and
A transparent composite conductor can then be obtained by removing the solvent.
透明高分子化合物基材上に混合物を塗布する方法として
は、スクリーン印刷塗布法、吹き付は法。Methods for applying the mixture onto the transparent polymer compound substrate include screen printing and spraying.
刷毛置注等があげられる。混合物は、透明高分子化合物
基材の片面のみに塗布してもよいし、また両面に塗布し
てもよい。Examples include brush injection. The mixture may be applied to only one side of the transparent polymer compound substrate, or may be applied to both sides.
溶媒の除去方法としては特に制限はなく、例えば真空下
に乾燥する方法、吸着剤による抽出方法。There are no particular limitations on the method for removing the solvent, such as drying under vacuum or extraction using an adsorbent.
加熱乾燥する方法等が採用される。A method such as heating and drying is adopted.
以下、実施例および比較例をあげて本発明をさらに詳細
に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例１
厚さ１００１１ｍのポリカーボネート膜の片面に、ＰＩ
ＴＮ ９０ Ｆ 、酸化インジウム粉末１５！ｉおよび
酸化スズ粉末５！ｉからなる混合物と塩化メチレン２５
ｍ１からなるスラリー状混合物を膜厚が０．０５μｍに
なるようにスクリーン印刷法で塗布した後、５０℃にて
真空乾燥して溶媒を除去した。Example 1 PI was applied on one side of a polycarbonate membrane with a thickness of 10011 m.
TN 90 F, indium oxide powder 15! i and tin oxide powder 5! a mixture consisting of i and methylene chloride 25
A slurry mixture consisting of m1 was applied by screen printing to a film thickness of 0.05 μm, and then vacuum dried at 50° C. to remove the solvent.
得られた複合膜の光透過率は６８％、電気伝導度は７
Ｘ １０−２８／ｍであった。また、この複合膜の塗布
面を消しゴム（ＳＳ５５０１）にて２５０回摺動しても
塗膜には異常がなく、耐スクラッチ性が良好であった。The resulting composite film had a light transmittance of 68% and an electrical conductivity of 7.
X 10-28/m. Moreover, even when the coated surface of this composite film was rubbed 250 times with an eraser (SS5501), there was no abnormality in the coating film, and the scratch resistance was good.
比較例１
実施例１と同じポリカーボネート膜の片面に、ＰＩＴＮ
９０９ 、酸化インジウム粉末１５ｇ、酸化スズ粉末
５ｇおよびエチルアルコール２５ｍ１からなるスラリー
状の混合物をスクリーン印刷法で塗布したところ、付着
性がほとんどなく、透明複合導電膜は得られなかった。Comparative Example 1 PITN was applied on one side of the same polycarbonate membrane as in Example 1.
909, 15 g of indium oxide powder, 5 g of tin oxide powder, and 25 ml of ethyl alcohol was applied by screen printing, but there was almost no adhesion and no transparent composite conductive film was obtained.
実施例２
厚さ１００μｍのポリエチレンテレフタレート膜の片面
上に、ＰＩＴＮ１６％、酸化インジウム粉末８Ｊ、酸化
スズ粉末７ｚおよびポリエチレンテレフタレート粉末０
．５１を良く混合した後で塩化メチレン１５ｍＡ！に入
れスラリー状にした混合物を膜厚が０，１μｍになるよ
うに刷毛置注で塗布した。次いで、常温で乾燥した後、
４０℃、真空下で塩化メチレンを除いた。得られた複合
膜は、光透過率が７５％、電気伝導度がＩ Ｘ １Ｏ−
２Ｓ ／ｃｍであった。Example 2 PITN 16%, indium oxide powder 8J, tin oxide powder 7z, and polyethylene terephthalate powder 0 were placed on one side of a 100 μm thick polyethylene terephthalate film.
．． After mixing 51 well, methylene chloride 15mA! The mixture was made into a slurry by pouring the mixture into a slurry, and the mixture was applied with a brush to a film thickness of 0.1 μm. Then, after drying at room temperature,
Methylene chloride was removed under vacuum at 40°C. The obtained composite film has a light transmittance of 75% and an electrical conductivity of I x 1O-
It was 2S/cm.
また、耐スクラッチテストを２５０回行なっても塗膜は
剥離しなかった。さらて、この複合膜をＬＩ ＢＦ４を
１モル／を含むアセトニトリル溶液中に設置し、対極に
白金を用いて通電しながらドープした後の電気伝導度は
５０ Ｓ／／ＣＩｒＬであり、光透過率は９０チであっ
た。Furthermore, the coating film did not peel off even after performing the scratch resistance test 250 times. Furthermore, this composite membrane was placed in an acetonitrile solution containing 1 mol/L of LIBF4, and after doping with platinum as a counter electrode while applying electricity, the electrical conductivity was 50 S//CIrL, and the light transmittance was It was 90chi.
実施例３
ＰＩＴＮ ６．２５１−、酸化スズ粉末ＩＰ、酸化カド
ミウム粉末０．５ｙ−およびポリ塩化ビニル粉末ＩＰを
ボールミルを用いて約１時間混合した。得られた混合物
を水Ｑ、 ｌ ｍｌと塩化メチレン０．９ ｍｌの混合
溶媒に混入しスラリー状混合物を得た。このスラリー状
混合物を厚さ１００μｍのポリ塩化ビニル膜の片面上に
０．１μｍの厚みになるように吹き付は法で塗布した後
、４０℃にて真空乾燥した。Example 3 PITN 6.251-, tin oxide powder IP, cadmium oxide powder 0.5y-, and polyvinyl chloride powder IP were mixed for about 1 hour using a ball mill. The obtained mixture was mixed into a mixed solvent of 1 ml of water Q and 0.9 ml of methylene chloride to obtain a slurry-like mixture. This slurry mixture was applied by spraying onto one side of a 100 μm thick polyvinyl chloride film to a thickness of 0.1 μm, and then vacuum dried at 40°C.
得られた複合膜は、光透過率が７３％、電気伝導度が１
×１０ ｓ／ｃｒｎであった。また、耐スクラッチテス
トを２００回行なっても塗膜には異常は認められなかっ
た。The resulting composite film has a light transmittance of 73% and an electrical conductivity of 1.
×10 s/crn. Further, no abnormality was observed in the coating film even after performing the scratch resistance test 200 times.
比較例２
厚さ１００μｍのプリエチレンテレフタレート膜の片面
上に酸化スズ−酸化インジウムの混合物を１５００Ｘに
なるように真空蒸着した。得られた複合膜の光透過率は
７０％、電気伝導度はｌＸ１Ｏ−４Ｓ／ｃｒｒＬであっ
た。また、この複合膜の耐スクラッチテストを行なった
ところ、１５０回摺動で酸化スズ−酸化インジウム膜の
一部が剥離した。Comparative Example 2 A mixture of tin oxide and indium oxide was vacuum-deposited on one side of a 100-μm-thick polyethylene terephthalate film to a thickness of 1500×. The resulting composite film had a light transmittance of 70% and an electrical conductivity of 1X1O-4S/crrL. Further, when a scratch resistance test was conducted on this composite film, part of the tin oxide-indium oxide film was peeled off after 150 sliding movements.
以上記述したように１本発明の方法によれば。 As described above, according to the method of the present invention.
高導電性であシ、光透過性、密着性、可とぅ性の良好な
透明複合導電体を得ることが可能となった。It has become possible to obtain a transparent composite conductor with high conductivity, good light transmittance, adhesion, and flexibility.
Claims (1)
溶媒、導電性高分子化合物および金属酸化物からなる混
合物または該基材を溶解可能な有機溶媒、導電性高分子
化合物、金属酸化物および前記透明高分子化合物基材を
構成する材料からなる混合物を塗布し、次いで溶媒を除
去することを特徴とする透明複合導電体の製造方法。A mixture of an organic solvent, a conductive polymer compound, and a metal oxide that can dissolve the base material, or an organic solvent, a conductive polymer compound, and a metal oxide that can dissolve the base material, on a transparent polymer compound base material. 1. A method for producing a transparent composite conductor, comprising applying a mixture of a material constituting the transparent polymer compound base material and the transparent polymer compound base material, and then removing the solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62103168A JPS63269415A (en) | 1987-04-28 | 1987-04-28 | Manufacture of transparent composite conductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62103168A JPS63269415A (en) | 1987-04-28 | 1987-04-28 | Manufacture of transparent composite conductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63269415A true JPS63269415A (en) | 1988-11-07 |
Family
ID=14346975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62103168A Pending JPS63269415A (en) | 1987-04-28 | 1987-04-28 | Manufacture of transparent composite conductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63269415A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005332754A (en) * | 2004-05-21 | 2005-12-02 | Kri Inc | Application liquid for transparent conductive film formation, and transparent conductive film |
| JP2006108008A (en) * | 2004-10-08 | 2006-04-20 | Sumitomo Metal Mining Co Ltd | Transparent conductive substrate and its manufacturing method |
| JP2006286418A (en) * | 2005-03-31 | 2006-10-19 | Tdk Corp | Transparent conductor |
| JPWO2006046431A1 (en) * | 2004-10-26 | 2008-05-22 | 旭硝子株式会社 | Inorganic coating composition, conductive coating film and method for forming conductive coating |
| WO2009054273A1 (en) * | 2007-10-26 | 2009-04-30 | Konica Minolta Holdings, Inc. | Transparent conducive film and method for producing the same |
-
1987
- 1987-04-28 JP JP62103168A patent/JPS63269415A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005332754A (en) * | 2004-05-21 | 2005-12-02 | Kri Inc | Application liquid for transparent conductive film formation, and transparent conductive film |
| JP2006108008A (en) * | 2004-10-08 | 2006-04-20 | Sumitomo Metal Mining Co Ltd | Transparent conductive substrate and its manufacturing method |
| JPWO2006046431A1 (en) * | 2004-10-26 | 2008-05-22 | 旭硝子株式会社 | Inorganic coating composition, conductive coating film and method for forming conductive coating |
| JP2006286418A (en) * | 2005-03-31 | 2006-10-19 | Tdk Corp | Transparent conductor |
| US7482056B2 (en) | 2005-03-31 | 2009-01-27 | Tdk Corporation | Transparent conductor |
| WO2009054273A1 (en) * | 2007-10-26 | 2009-04-30 | Konica Minolta Holdings, Inc. | Transparent conducive film and method for producing the same |
| US8456005B2 (en) | 2007-10-26 | 2013-06-04 | Konica Minolta Holdings, Inc. | Transparent conductive film and method for producing the same |
| JP5353705B2 (en) * | 2007-10-26 | 2013-11-27 | コニカミノルタ株式会社 | Transparent conductive film and method for producing the same |
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